Two broad bands are usually found in the Raman spectrum of many Te-based chalcogenides, which include binary compounds, like ZnTe, CdTe, HgTe, GaTe, GeTe, SnTe, PbTe, GeTe2, As2Te3, Sb2Te3, Bi2Te3, NiTe2, IrTe2, TiTe2, as well as ternary compounds, like GaGeTe, SnSb2Te4, SnBi2Te4, and GeSb2Te5. Many different explanations have been proposed in the literature for the origin of these two anomalous broad bands in tellurides, usually located between 119 and 145 cm-1. They have been attributed to the own sample, to oxidation, to the folding of Brillouin-edge modes onto the zone center, to the existence of a double resonance, like that of graphene, or to the formation of Te precipitates. In this paper, we provide arguments to demonstrate that such bands correspond to clusters or precipitates of trigonal Te in form of nanosize or microsize grains or layers that are segregated either inside or at the surface of the samples. Several mechanisms for Te segregation are discussed and sample heating caused by excessive laser power during Raman scattering measurements is emphasized. Finally, we show that anomalous Raman modes related to Se precipitates also occur in selenides, thus providing a general vision for a better characterization of selenides and tellurides by means of Raman scattering measurements and for a better understanding of chalcogenides in general.
We report results of micro-Raman spectroscopy investigation of the "graphene-like" mechanically exfoliated single-crystal bismuth telluride films with the thickness ranging from a few-nm-range to bulk limit. It is found that the optical phonon mode A1u, which is not-Raman active in bulk bismuth telluride crystals, appears in the atomically-thin films due to crystal-symmetry breaking. The intensity ratios of the out-of-plane A1u and A1g modes to the in-plane Eg mode grow with decreasing film thickness. The evolution of Raman signatures with the film thickness can be used for identification of b…
The origin of the anomalous anharmonic lattice dynamics of lead telluride is investigated using molecular dynamics simulations with interatomic force constants (IFCs) up to quartic terms obtained from first principles. The calculations reproduce the peak asymmetry of the radial distribution functions and the double peaks of transverse optical phonon previously observed with neutron diffraction and scattering experiments. They are identified to be due to the extremely large nearest-neighbor cubic IFCs in the [100] direction. The outstanding strength of the nearest-neighbor cubic IFCs relative t…
The quantum anomalous Hall effect (QAHE) is an exotic quantum phenomenon originating from dissipation-less chiral channels at the sample edge. While the QAHE has been observed in magnetically doped topological insulators (TIs), exploiting magnetic proximity effect on the TI surface from adjacent ferromagnet layers may provide an alternative approach to the QAHE by opening an exchange gap with less disorder than that in the doped system. Nevertheless, the engineering of a favorable heterointerface that realizes the QAHE based on the magnetic proximity effect remains to be achieved. Here, we rep…
Two-dimensional (2D) materials possess great potential for flexible devices, ascribing to their outstanding electrical, optical, and mechanical properties. However, their mechanical deformation property and fracture mechanism, which are inescapable in many applications like flexible optoelectronics, are still unclear or not thoroughly investigated due methodology limitations. In light of this, such mechanical properties and mechanisms are explored on example of gallium telluride (GaTe), a promising optoelectronic candidate with an ultrahigh photo-responsibility and a high plasticity within 2D …
A detailed high pressure study is carried out on 1T$^\prime$ MoTe$_{2}$ using X-ray diffraction(XRD) and Raman spectroscopy measurements upto about 30.5 GPa. High pressure XRD measurements show no structural transition. All the lattice parameters exhibit anomalous changes in the pressure region 8.4 to 12.7 GPa. Compressibility of the sample is found to be reduced by almost four times above 12.7 GPa with respect to that below 8.4 GPa. The anomalies in the Raman mode corresponding to the out of plane vibrations of Mo atoms sitting in the unit cell surface indicate a strong electron phonon coupli…
Topological Weyl semimetals (WSMs) have attracted widespread interests due to the chiral Weyl fermions and surface Fermi arcs that enable unique optical and transport phenomena. In this work, we present angle-resolved Raman spectroscopy of TaP, a prototypical noncentrosymmetric WSM, for five excitation wavelengths ranging from 364 to 785 nm. The Raman active modes, $A_1$, $B_1^1$, and $B_1^2$ modes, exhibit two main unique features beyond the conventional Raman theory. First, the relative intensities of Raman active modes change as a function of the excitation wavelength. Second, angle-resolve…
Stokes and anti-Stokes Raman scattering are performed on atomic layers of hexagonal molybdenum ditelluride (MoTe2), a prototypical transition metal dichalcogenide (TMDC) semiconductor. The data reveal all six types of zone center optical phonons, along with their corresponding Davydov splittings, which have been challenging to see in other TMDCs. We discover that the anti-Stokes Raman intensity of the low energy layer-breathing mode becomes more intense than the Stokes peak under certain experimental conditions, and find the effect to be tunable by excitation frequency and number of atomic lay…
Time-resolved Raman spectroscopy has been applied to probe the anharmonic coupling and electron-phonon interaction of optical phonons in graphite. From the decay of the transient anti-Stokes scattering of the G-mode following ultrafast excitation, we measured a lifetime of 2.2+/-0.1ps for zone-center optical phonons. We also observed a transient stiffening of G-mode phonons, an effect attributed to the reduction of the electron-phonon coupling for high electronic temperatures.
The resonance effects on the Raman spectra from 5 to 900 cm-1 of few-layer MoS2 thin films up to 14-layers were investigated by using six excitation energies. For the main first-order Raman peaks, the intensity maximum occurs at ~2.8 eV for single layer and at ~2.5 eV for few-layer MoS2, which correspond to the band-gap energy. At the excitation energy of 1.96 eV, several anomalous behaviors are observed. Many second-order peaks are anomalously enhanced even though the main first-order peaks are not enhanced. In the low-frequency region (<100 cm-1), a broad peak centered at ~38 cm-1 and its se…
The potential of silicon nanowires (SiNWs), (diameter < 10 nm) to transform into rigid bundle-like structures with distinct phonon confinement under high pressure (<= 15 GPa), instead of amorphising as per previous reports, is demonstrated using in-situ Raman spectroscopy. The newly observed splitting of the second order transverse optical (2TO) Raman mode into 2TO(L) and 2TO(W) phonon modes at >= 5 GPa establishes a highly anisotropic and mode-dependent pressure response of these SiNWs. Properties of the novel structures are superior compared to other nano-structured silicon and bulk-Si in te…
We investigated polarization dependence of the Raman modes in black phosphorus (BP) using five different excitation wavelengths. The crystallographic orientation was determined by comparing polarized optical microscopy with high-resolution transmission electron microscope analysis. In polarized Raman spectroscopy, the B2g mode shows the same polarization dependence regardless of the excitation wavelength or the sample thickness. On the other hand, the Ag1 and Ag2 modes show a peculiar polarization behavior that depends on the excitation wavelength and the sample thickness. The thickness depend…
Typical Raman spectra of transition metal dichalcogenides (TMDs) display two prominent peaks, E2g and A1g, that are well separated from each other. We find that these modes are degenerate in bulk WSe2 yielding one single Raman peak. As the dimensionality is lowered, the observed peak splits in two as a result of broken degeneracy. In contrast to our experimental findings, our phonon dispersion calculations reveal that these modes remain degenerate independent of the number of layers. Interestingly, for minuscule biaxial strain the degeneracy is preserved but once the crystal symmetry is broken…
The temperature dependence of the first-order phonon mode of single crystal of Silicon (Si) is determined by Raman scattering in a broad temperature range of 4-623 K. Our studies reveal the anomalous red-shift of the Raman active phonon mode at temperature (~ 50 K) attributed to the anomalous expansion of Si in the low temperature region. Silicon shows negative thermal expansion below 120 K, however, odd behaviour is also observed at very low temperatures i.e., softening of the Si crystal is detected below 40 K. This peculiar behaviour of Si is described by the anomalous phonon anharmonicity o…
The layered dichalcogenide MoS2 has many unique physical properties in low dimensions. Recent experimental Raman spectroscopies report an anomalous blue shift of the in-plane E2g1 mode with decreasing thickness, a trend that is not understood. Here, we combine experimental Raman scattering and theoretical studies to clarify and explain this trend. Special attention is given to understanding the surface effect on Raman frequencies by using a force constants model based on first-principles calculations. Surface effects refer to the larger Mo-S force constants at the surface of thin film MoS2, wh…
Tungsten ditelluride (WTe2) is a layered material that exhibits excellent magnetoresistance and thermoelectric behaviors, which are deeply related with its distorted orthorhombic phase that may critically affect the lattice dynamics. Here, for the first time, we present comprehensive characterization of the Raman spectroscopic behavior of WTe2 from bulk to monolayer using experimental and computational methods. We discover that mono and bi-layer WTe2 can be easily identified by Raman spectroscopy since double or single Raman modes that are observed in higher-layer WTe2 are substantially suppre…
We report a comprehensive temperature dependent Raman measurements on three different phases of monolayer WS2 from 4K to 330K in a wide spectral range. Our studies revels the anomalous nature of the first as well as the higher order combination modes reflected in the disappearance of the few modes and anomalous temperature evaluation of the phonon self-energy parameters attributed to the detuning of resonance condition and development of strain due to thermal expansion mismatch with the underlying substrate. Our detailed temperature dependence studies also decipher the ambiguity about assignme…
Molybdenum disulfide (MoS2) of single and few-layer thickness was exfoliated on SiO2/Si substrate and characterized by Raman spectroscopy. The number of S-Mo-S layers of the samples was independently determined by contact-mode atomic-force microscopy. Two Raman modes, E12g and A1g, exhibited sensitive thickness dependence, with the frequency of the former decreasing and that of the latter increasing with thickness. The results provide a convenient and reliable means for determining layer thickness with atomic-level precision. The opposite direction of the frequency shifts, which cannot be expl…
Electronic structure near Fermi level of Pr2CoFeO6 (at 300 K) was investigated by X-ray photoemission spectroscopy (XPS) technique. All three cations, i.e., Pr, Co and Fe were found to be trivalent in nature. XPS analysis also suggested the system to be insulating in nature. Moreover, Raman spectroscopy study indicated the random distribution of the B-site ions (Co/Fe) triggered by same charge states. In temperature-dependent Raman study, the relative heights of the two observed phonon modes exhibited anomalous behaviour near magnetic transition temperature TN~270 K, thus indicating towards in…
Layered inorganic materials, such as the transition metal dichalcogenides (TMDs), have attracted much attention due to their exceptional electronic and optical properties. Reliable synthesis and characterization of these materials must be developed if these properties are to be exploited. Herein, we present low-frequency Raman analysis of MoS2, MoSe2, WSe2 and WS2 grown by chemical vapour deposition (CVD). Raman spectra are acquired over large areas allowing changes in the position and intensity of the shear and layer-breathing modes to be visualized in maps. This allows detailed characterizat…
Charge density wave (CDW) is a unique phenomenon mostly realized in two-dimensional (2D) metallic layered transition metal dichalcogenides (TMDCs). Here, we report on Raman spectroscopy of single crystal 1T-VSe2 and observed signature of commensurate CDW (C-CDW) and incommensurate (I-CDW) transition, in the temperature range of 50-120 K. The room temperature Raman spectra showed a sharp A1g mode ~ 206 cm-1 along with two new weak and broad Raman modes associated to Eg mode ~ 257 cm-1 and two-phonon mode (2ph) ~ 332 cm-1. The onset of I-CDW and C-CDW is estimated from resistance measurements su…
We report inelastic light scattering experiments on superconductor Ce0.6Y0.4FeAsO0.8F0.2 from 4K to 300K covering the superconducting transition temperature Tc ~ 48.6K. A strong evidence of the superconductivity induced phonon renormalization for the A1g phonon mode near 150 cm-1 associated with the Ce/Y vibrations is observed as reflected in the anomalous red-shift and decrease in the linewidth below Tc. Invoking the coupling of this mode with the superconducting gap, the superconducting gap (2) at zero temperature is estimated to be ~ 20 meV i.e the ratio is ~ 5, suggesting Ce0.6Y0.4FeAsO0.8…
Polarized Raman scattering spectra of the K_xCo_{2-y}Se_2 single crystals reveal the presence of two phonon modes, assigned as of the A_{1g} and B_{1g} symmetry. Absence of additional modes excludes the possibility of vacancy ordering, unlike in K_xFe_{2-y}Se_2. The ferromagnetic (FM) phase transition at T_c\approx 74 K leaves a clear fingerprint on the temperature dependence of the Raman mode energy and linewidth. For T>T_c the temperature dependence looks conventional, driven by the thermal expansion and anharmonicity. The Raman modes are rather broad due to the electron-phonon coupling incr…
We report the observation of an intense anomalous peak at 1608 cm$^{-1}$ in the Raman spectrum of graphene associated to the presence of chromium nanoparticles in contact with graphene. Bombardment with an electron beam demonstrates that this peak is distinct from the well studied D$'$ peak appearing as defects are created in graphene; the new peak is found non dispersive. We argue that the bonding of chromium atoms with carbon atoms softens the out-of-plane optical (ZO) phonon mode, in such a way that the frequency of its overtone decreases to $2ω_{\rm ZO}\simω_{\rm G}$, where $ω_{\rm G}$=158…
The vibrational spectroscopy of semiconductor nanostructures can provide important information on their structure. In this work, experimental Raman and infrared spectra are compared with vibrational spectra of CdSe/CdS core/shell nanoplatelets calculated from first principles using the density functional theory. The calculations confirm the two-mode behavior of phonon spectra of nanostructures. An analysis of the experimental spectra reveals the absence of modes with a high amplitude of vibrations of surface atoms, which indicates their strong damping. Taking into account the difference in the…
We report high pressure X-ray diffraction and a detailed systematic Raman measurements on $ReS_2$ sample, which is mechanically exfoliated from a single crystal. A few new Bragg peaks are observed to emerge above 6 GPa indicating a structural transition from distorted $1T$ to distorted $1T$$^{\prime}$ in triclinic structure. The same is corroborated by appearance of new Raman modes in the same pressure range. Softening of the Raman modes corresponding to $Re$ atom vibrations are observed in the distorted $1T$$^{\prime}$ phase in the pressure range 15-25 GPa. In the same pressure range the anom…
In the orbitally ordered, quasi-one dimensional Heisenberg antiferromagnet KCuF3 the low-energy Eg and B1g phonon modes show an anomalous softening (25% and 13%) between room temperature and the characteristic temperature T_S = 50 K. In this temperature range a freezing-in of F ion dynamic displacements is proposed to occur. In addition, the Eg mode at about 260 cm-1 clearly splits below T_S. The width of the phonon lines above T_S follows an activated behavior with an activation energy of about 50 K. Our observations clearly evidence a reduction of the structural symmetry below T_S and indica…
We determine the nature of coupled phonons and magnetic excitations in AlFeO3 using inelastic light scattering from 5 K to 315 K covering a spectral range from 100-2200 cm-1 and complementary first-principles density functional theory-based calculations. A strong spin-phonon coupling and magnetic ordering induced phonon renormalization are evident in (a) anomalous temperature dependence of many modes with frequencies below 850 cm-1, particularly near the magnetic transition temperature Tc ~ 250 K, (b) distinct changes in band positions of high frequency Raman bands between 1100-1800 cm-1, in p…
We have carried out a detailed experimental investigation on CuO using dielectric constant, ac resistance, Raman spectroscopy and X-ray diffraction measurements at high pressures and room temperature. Both dielectric constant and dielectric loss show an anomalous peak in the pressure range 3.4-4 GPa indicating a ferroelectric transition. Raman studies show anomalous behaviour of the Ag mode with a slope change in the mode frequency and a minimum in the mode FWHM at 3.4 GPa indicating a strong spin phonon coupling along [1 0 -1] direction. A step like behaviour in the intensity of the Ag mode i…
A detailed high pressure investigation is carried out on $Fe_4Nb_2O_9$ using angle resolved x-ray diffraction and Raman spectroscopy measurements. We find a structural transition from the ambient trigonal phase to a monoclinic phase above 8.8 GPa. The structural transition is assumed to be driven by a large distortion of $Nb-O_6$ octahedra as seen from x-ray diffraction analysis and a large pressure dependence of $Nb-O_6$ octahedra breathing Raman mode. Anomalous behaviour of Raman modes and increase in the phonon life time at the phase transition pressure indicate a trigonal paramagnetic phas…
Multiferroics possess two or more switchable states such as polarization, magnetization, etc. Phonon excitations in multiferroic phase are strongly modified by magnetoelectric coupling, spin-phonon coupling, and anharmonic phonon-phonon interactions. Here, we have investigated the correlation between phonons and multiferroic order parameters in hexagonal BaMO3: M = Ti1-x(Mn/Fe)x systems using powder x-ray diffraction (PXRD), Raman spectroscopic, and magnetic measurements. The structural transformation from a polar tetragonal to a non-polar 6H-type hexagonal phase is observed as a function of d…
Detailed Raman spectroscopy studies on polycrystalline Sr1-xPrxTiO3 (x=0.01, 0.025, 0.05, 0.075, 0.09, 0.13, 0.15, 0.17) samples are reported elucidating the microscopic mechanism of relaxor ferroelectrics. The polar mode was observed upto very high temperature ~1000 K suggesting that the dipoles exists at temperatures well above the characteristic relaxor temperatures and they develop a short range correlation at 505 K leading to formation of PNRs. The TO2 polar mode showed anomalous softening in cooling below T~505 K supporting the growth of PNRs. Fano resonance is reported in the Pr doped c…
We report on the temperature dependent Raman spectroscopic studies of orthorombic distorted perovskite YCrO3 in the temperature range of 20-300K. Temperature dependence of DC-magnetization measurement under field cooled and zero field cooled modes confirmed the transition temperature (TN ~142K) and anomalous characteristic temperature (T* ~60K), above which magnetization tends to saturate. Magnetization isotherm recorded below TN at 125K shows clear loop opening without magnetization saturation up to 20kOe, indicating the coexistence of antiferromagnetic (AFM) interaction with weak ferromagnet…
We have carried out temperature-dependent x-ray diffraction and Raman scattering experiments on powder $Cs_3Bi_2Br_9$. Trigonal to monoclinic structural transition at around 95 K is discussed and shown to be driven by the softening of the soft mode. We propose a model to describe the dynamics of the incomplete soft-mode. Raman scattering experiments demonstrate the origin of the soft mode to the rocking motions of Br atoms that participate to form $BiBr_6$ octahedra, which correlates the reported theoretical calculations. Some of the Raman mode frequencies exhibit anomalous temperature depende…
We have studied spectral evolution of the $E_u^1$ phonon line of a topological insulator Bi$_{2-x}$Sr$_x$Se$_3$ with temperature. Unlike the Raman-active phonons, the $E_u^1$ mode demonstrates softening upon cooling the crystal, and the corresponding spectral line acquires a pronounced Fano-like shape at temperatures $T\lesssim100$ K. We interpret the latter effect as a signature of specific coupling of the bulk infrared active phonons to surface Dirac electrons. Using coherent resonant excitation of the $E_u^1$ mode as a surface sensitive tool, we have detected softening of the surface counte…
New plasmon-like mode in PdTe$_{2}$: Raman scattering and memory function study
Physical Research Laboratory（物理研究实验室）；Indian Institute of Technology, Gandhinagar（印度理工学院甘地纳加尔分校）；School of Physical Sciences, Indian Institute of Technology Mandi（印度理工学院曼迪校物理科学学院）
Raman signatures of a non-reciprocal magnetic phase transition in Ca$_2$RuO$_4$
University of Erlangen-Nürnberg（埃尔朗根-纽伦堡大学）；University of Trieste（的里雅斯特大学）；CNR-SPIN, University of Salerno（萨莱诺大学 CNR-SPIN 研究所）；Elettra Sincrotrone Trieste（的里雅斯特电子同步辐射中心）；CNR-Istituto Officina dei Materiali (IOM)（CNR 材料工坊研究所）
Twisted bilayer graphene (tBLG) provides us with a large rotational freedom to explore new physics and novel device applications, but many of its basic properties remain unresolved. Here we report the synthesis and systematic Raman study of tBLG. Chemical vapor deposition was used to synthesize hexagon- shaped tBLG with a rotation angle that can be conveniently determined by relative edge misalignment. Superlattice structures are revealed by the observation of two distinctive Raman features: folded optical phonons and enhanced intensity of the 2D-band. Both signatures are strongly correlated w…
Twisted bilayer graphene (tBLG) devices with ion gel gate dielectrics are studied using Raman spectroscopy in the twist angle regime where a resonantly enhanced G band can be observed. We observe prominent splitting and intensity quenching on the G Raman band when the carrier density is tuned away from charge neutrality. This G peak splitting is attributed to asymmetric charge doping in the two graphene layers, which reveals individual phonon self-energy renormalization of the two weakly-coupled layers of graphene. We estimate the effective interlayer capacitance at low doping density of tBLG …
The charge-density wave (CDW) phase is often accompanied by the condensation of a soft acoustic phonon mode, giving rise to lattice distortion and charge density modulation. This picture was challenged for the recently discovered kagome metal CsV$_3$Sb$_5$, based on the evidence of absence of soft phonons. Here we report the observation of Raman-active CDW amplitude modes in this material, which are collective excitations typically thought to emerge out of frozen soft phonons. The amplitude modes strongly hybridize with other superlattice modes, imparting them with clear temperature-dependent …
